Polyazo-dyestuffs



-. 'Claims priority,

United States Patent Oflice 2,758,109 Patented Aug. 7, 1956 2,758,109 HPOLYAZO-DYESTUFFS Richard Huss, Wilhelm Happe, Arthur Siebert, and JosefWeissert, Frankfurt am Main, Germany, assignors to Farbwerke HoechstAktiengesellschaft vormals Meister Lucius und Brlming, Frankfurt am MainHochst, Germany, a German company No Drawing. Application December 9,1952, Serial No. 325,016 application Germany December 22, 1951 7"Claims. (Cl. 260-469) The present invention relates topoly-azo-dyestuifs; more particularly it relates to thepoly-azo-dyestufi's cor- :responding to the following formula X standsfor one of the groups and Y represents hydrogen or the sulfonic acidgroup.

We have found that poly-azo-dyestufis dyeing leather valuable browntints are obtained by coupling the monoazo-dyestuif from a diazotized1-amino-8-hydroxynaphthalenemono or di-sulfonic acid or the 3'- or4'-aminobenzoylamino derivative thereof and 1.3-dihydroxy-benzene with 2mols of any diazo compound, at least one of which is a diazotizedamino-diphenylamine-sulfonic acid.

The new dyestutfs have a high coloring strength, they are very readilysoluble in water and resistant to inorganic and organic acids. They arealso insensitive to alkalies and formaldehyde." The dyestuffs dyechrometanned leather and leather tanned with vegetable and synthetictanning agents deep brown tints and they are firmly fixed on the fiber.

In Swiss Patent No. 117,476 a trisazo-dyestuif is described having thecomposition l-amino-Z-methylbenzene-4-sulfonic acid1:3-dihydroxy-benzene l-amino-S- hydroxy naphthalene-3 :6-disulfonicacid 1-amino-4-nitrobenzene which dyes leather a yellowish brown tint,the flesh-side of the leather being dyed a much yellower with thisdyestufi, the new dyestuffs molecule an amino-diphenylaminesulfonic acidinstead of 1-amino-2-methylbenzene-4-sulfonic acid, are distinguished bytheir particularly fine tints and by an improved solubility. As comparedwith the known analogous dyestuffs which contain as final component 1amino 2 methyl-3-chlorobenzene-5-su1fonic acid,1-aminobenzene-4-sulfonic acidor l-aminonaphthalene-4-sulfom'c acid, thedyestufl s obtainable by the present invention likewise involve theadvantage of a considerably improved solubility.

Moreover, the known dyestuffs of the following compositionl-aminobenzene-tsulfonic acid- I:3-dihydroxyis the radical of adiphenylamine-sulfonic acid,

2 benzene 1 amino-8-hydroxy-naphthalene-4-sulfonic acid or 1amino-8-hydroxy-naphthalene-4:6-disulfonic acid 1-amino-4-nitrobenzeneare essentially gards fastness to alkalies, to the new dyestuffs whichcontain an amino-diphenylamine-sulfonic acid instead of 1-aminobenzene-4-sulfonic acid.

The dyestutf 1-amino-2-hydroxy-3:S-dinitrobenzene 1:3 dihydroxy-benzene1 amino-8-hydroxy-naphthalene 3 :6 disulfonic acidl-amino-4-nitrobenzene de-' scribed in Swiss Patent No. 116,360 dyesleather dark to be prepared while observing special precautions on Thehigh sensitiveness of the dyestuff powder has also to be taken intoconsideration In the manufacturing process it is hardly possible toobtain products yielding uniform dyeings, since shades turning to violetwhich are undesired in dyeing leather are frequently produced. Byexchanging the 1-amino-2-hydroxy-3:S-dinitrobenzene for anamino-diphenylamine-sulfonic acid according to the present invention,dyestuffs are obtained whose combustibility is considerably reduced andwhich, moreover, are distinguished by an improved solubility andfastness to alkalies.

The new dyestuffs, therefore, constitute a valuable enrichment in thefield of the hitherto known brown leather dyestuifs.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by Weight unlessotherwise stated, and the relationship of parts by weight to parts byvolume being the same as that of the kilogram to the liter:

Example I 34.1 parts of 1-amino-8-hydroxy-naphthalene-3:6-disulfonicacid (mono-sodium salt) are dissolved with 10.5 parts by volume ofsodium hydroxide solution of 33 per cent strength and diazotized with 20parts by volume of a 5 N-sodium nitrite solution in the presence ofparts by volume of 5 N-hydrochloric acid. After the addition of asolution of 11 parts of 1:3-dihydroxy-benzene in 100 parts by volume ofwater, 18 parts by volume of sodium hydroxide solution of 33 per cent.strength are added dropwise in the course of minutes. When the couplingis complete at the pH-value of 6, the diazo suspension of 26.4 parts of4-amino-diphenylamine-2-sulfonic acid and such a quantity of 2 N-sodiumhydroxide solution are added at 15 C., that the coupling takes place atthe pH-value of 9. The disazo-dyestutf is stirred for one night. Theclarified diazo solution of 15.2 parts of 1-arnino-4-nitrobenzene andsuch a quantity of 2 N- sodium hydroxide solution are then addeddropwise in the course of /2 hour until the pH-value of 4 has beenattained. When the coupling is complete, the trisazodyestufi is saltedout With common salt, filtered with suction and dried. It is ablack-brown powder which dyes chrome-tanned leather or leather tannedwith vegetable or synthetic tanning agents deep red-brown tints. Thedyestuff, which is also well suitable for brush dyeing, is resistant toacids, alkalies, and formaldehyde and possesses a good fastness tolight. It corresponds to the following formula Example 2 The diazocompound hydroxy-naphthalene-3 6- salt) is combined at a p 1 :3-dihydroXy-benzene.

and 220 parts by volume of sodium 33 per cent. strength are alkalinesolution of the disazo-dyestuii temperature between 10 blacktrisazo-dyestuif dyes the various drum dyeing, brush dyeing or spray andformaldehyde.

H-value of 6 with 110 parts of from 341 parts of 1-amino-8- disulfonicacid (mono-sodium To the alkaline solution of diazotizedl-amino-S-hydroxy-n acid, 1 3-dihydroXy-benzene Example 3 thedisazo-dyestuff from aphthalene-3 6-disulfonic and diazotized4-amino-di- The diazo-suspension of 309 5 phenylamine-Z-sulfonic acidobtainable as described in parts of4-amino-4-nitrodiphenylamine-2'-sulfonic acid Example 1 there are addedfirst 20 parts of crystallized hydroxide lutio of sodium acetate andthen, in small portions, the diazoth poured i t th l ti f suspensionfrom 30.9 parts of 4-amino-4-nitrodiphenylthe mono-azo-dyestuff thusobtained, whereby apH-value 10 mine-T- Mf nic acid. The pH-value of thecoupling I of 8 9 is attained w the Cgupling is complete, the mediumdecreases thereby to 4. After stirring for 1 hour,

Obtained is mixed the mixture is salted out with common salt, filteredwith With 20 parts of crystallized sodium acetate, and the clarisumo andThe dark'brown powdfir dyes leather *1 fied diaZo-solution of 172.5parts of 1-amino-2-chl0r0-4- p i vanous Processes l tints Whlch arenitrobenzene is then slowly added to the mixture at a 15 g ig g y verygood fastness tohghnformaldehydei and 15 o Stirring is con- Bi i i t cli zin iii in this exam 1e the 30 9 arts of 4-aminotinued for 1 hour andthe mixture is then salted out with 4, nitrodipheiylimine z, Sulfgnicacid' 5 264 parts of common Salt filtered with Suctlon and The brown4-amino-diphenylamine-Z-sulfonic acid, there is obtained kmdsfJf leatherY a dyestutf of similar properties.

dyemg yellowish 20 In the following table are given a number of otherazobrown tints of very good fastness to light, to acids, alkaliesdyestuffs of this invention which dye leather similar tints and impartto leather the same good fastness properties:

Constitution Tint 1-Amlno-2-chlor0-4-nitrobenzene 1 amino 8 hydroxynaphtha 1ene4-suli0nic acid 4-amin0-4-m'tr0diphenylamine-2'-sulf0nicacid l-arnino-Z-chloro-4-nitrobenzene 1 amino 8 hydroxy naphthalene-fi-sulfonic acid 1-amin0-4-nitro-benzene 1 amino 8 hydroxy naphthalene-4:6-disu1ionic acid it-amino-diphenylamine-2-sulfonic acid1-arnin0-2-chl0r0-4-nitrobenzcnc 1 (4 aminobenzoylamino) 8 hydroxynapthalene 3:6 di sulfonic acid 1-amin0-2-chl0rO-4-nltr0benzene1-(3-aminobenzoylamino)-8-hydroxy-naphthalene-3: 6 disul ionic acidl-amino-2-chloro-4-nitrobcnzene 1 amino 8 hydroxy-naphthalene-3zB-disulf0nic acid4-amino-4-chlorc-diphenylaminc-2-sultonic acidl-amino-2-nitr0-4-methylbenzene 1 amino 8 hydroxy -naphthalone-3:6-disulfonic acid 4-amino-2: 4'-dlnltro-diphenyl-amine-6-sulf0nic acid 1 amino 8 hydroxy naphtha lene-3:6-disultonic acidl-aminobenzene-d-sulfonic acid l-arninobenzenei-sulfonic acidl-arnino-S-hydroxy-naphthalane-3: G-disulionic acid4-arnin0-4'-nitrodiphenylamine-2-sulfonic acid 4 -amin0diphenyl amine 2-suli'onic acid 1-amin0-8-hydroxy-naphtha- 1ene-3:6-disulionic acid4-amin0-1:1'-azo-benzene-4'-sulfonic acid 4 aminodiphenyl amine 2sulfonic acid 1 amino 8 hydroxy naphtha lcne-3z6-disu1fonic acidLamino-naphthalene-M'Y) -sultonic acid (mixture of Oleves acids)1-amino-2-methyl-3-chl0robenzenefi-sulfonlc acid l-emino 8 hydroxynaphtha- 4 amino 4 -nitro diphenylamine 2' sulfonic acid 1 amino 8hydroxy naphtha 1ene-3: fi-disulfonic acid 1:3- dihydroxy benzene1:3-dihydroxy-benzene 1:3 dihydroxy -benzene 1:3 -dihydroxy-benzene 1:3-dihydroxy-benzene 1:3- dihydroxy -benzenc 1: 3-dihydroxy -benzene 1 :3-dihydroxy-benzene 1 :3 dihydroxy benzene 1:3 -dihydroxy-benzene 1:3dihydroxy benzene 1:3 dihydroxy -benzene 1:3-dihyd1'oxy-benzeneyellowish brown.

reddish brown.

bluish brown.

red-brown.

reddish yellowcrown.

yellow-brown.

bluish redbrown.

deep red-brown.

dark red-brown.

.5 We claim: 1. Poly-azo-dyestutfs corresponding to the followinggeneral formula 2-. Poly-azo-dyestufis corresponding to the followinggeneral formula OH MGM;

;; wherein R and R1 each represents a member selected from SOgH whereinR and R1 each represents a member selected from the group consisting ofradicals of the benzene and naphthalene series, at least one of which isthe radical of a 20 diphenylarnine-sulfonic acid, and Y stands for amember of the group consisting of hydrogen and the sulfonic acid and Ystands for a member of the group consisting of gt 'lhe poly-azo-dyestuffcorresponding to the following hydrogen and the sulfonic acid group.formula OH N=N OH o,N-N=N- N=NO-NHO Hmsso,H AOiH 4. Thepoly-azo-dyestulf corresponding to the following 5. Thepoly-azo-dyestuff corresponding to the following formula 6. Thepoly-azo-dyestulf corresponding to the following: formula onN=NONHQ-N0i:

7. The poly-azo-dyestufi corresponding to the i01lowing formula H035S0311 SOxH References Cited in the file of this patent UNITED STATESPATENTS 117,476 Switzerland Nov. 1, 1926

1. POLY-AZO-DYESTUFFS CORRESPONDING TO THE FOLLOWING GENERAL FORMULA